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DOE OSTI2024

Fluid inertia controls mineral precipitation and clogging in pore to network-scale flows

Mineral precipitation caused by fluid mixing presents complex control and predictability challenges in a variety of natural and engineering processes, including carbon mineralization, geothermal energy, and microfluidics. Precipitation dynamics, particularly under the influence of fluid flow, remain poorly understood. Combining microfluidic experiments and three-dimensional reactive transport simulations, we demonstrate that fluid inertia controls mineral precipitation and clogging at flow intersections, even in laminar flows. We observe distinct precipitation regimes as a function of Reynolds number (Re). At low Reynolds numbers (Re < 10), precipitates form a thin, dense layer along the mixing interface, which shuts precipitation off, while at high Reynolds numbers (Re > 50), strong three-dimensional flows significantly enhance precipitation over the entire intersection, resulting in rapid clogging. When injection rates from two inlets are uneven, flow symmetry-breaking leads to unexpected flow bifurcation phenomena, which result in enhanced concurrent precipitation in both downstream channels. Finally, we extend our findings to rough channel networks and demonstrate that the identified inertial effects on precipitation at the intersection scale are also present and even more dramatic at the network scale. This study sheds light on the fundamental mechanisms underlying mixing-induced mineral precipitation and provides a framework for designing and optimizing processes involving mineral precipitation.

Science & Technology - Other Topics↗

DOE OSTI2017

Changes in Temperature and Precipitation Extremes in Superparameterized CAM in Response to Warmer SSTs

Subdaily temperature and precipitation extremes in response to warmer SSTs are investigated on a global scale using the superparameterized (SP) Community Atmosphere Model (CAM), in which a cloud-resolving model is embedded in each CAM grid column to simulate convection explicitly. Two 10-yr simulations have been performed using present climatological sea surface temperature (SST) and perturbed SST climatology derived from the representative concentration pathway 8.5 (RCP8.5) scenario. Compared with the conventional CAM, SP-CAM simulates colder temperatures and more realistic intensity distribution of precipitation, especially for heavy precipitation. The temperature and precipitation extremes have been defined by the 99th percentile of the 3-hourly data. For temperature, the changes in the warm and cold extremes are generally consistent between CAM and SP-CAM, with larger changes in warm extremes at low latitudes and larger changes in cold extremes at mid-to-high latitudes. For precipitation, CAM predicts a uniform increase of frequency of precipitation extremes regardless of the rain rate, while SP-CAM predicts a monotonic increase of frequency with increasing rain rate and larger change of intensity for heavier precipitation. The changes in 3-hourly and daily temperature extremes are found to be similar; however, the 3-hourly precipitation extremes have a significantly larger change than daily extremes. The Clausius–Clapeyron scaling is found to be a relatively good predictor of zonally averaged changes in precipitation extremes over midlatitudes but not as good over the tropics and subtropics. The changes in precipitable water and large-scale vertical velocity are equally important to explain the changes in precipitation extremes.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Quantifying Heavy Precipitation throughout the Entire Tropical Cyclone Life Cycle

Abstract Tropical cyclones (TCs) and their associated precipitation can have devastating impacts on the areas affected, with outcomes ranging from mudslides to inland flash flooding. Previous studies have used a fixed radius around the TC to isolate storm-related precipitation. One previous study instead used a dynamic radius of 8 m s −1 winds, but the wind field of the TC can deteriorate or shift quickly after landfall or the onset of extratropical transition (ET). This study uses a dynamical radius derived from the 500-hPa geopotential height in and around the TC to define TC- and post-tropical cyclone (PTC)-related heavy precipitation, allowing for the analysis of precipitation with tropical origins after the official demise of the original TC. Climatologies are constructed, indicating a maximum in TC- and PTC-related heavy precipitation in the west North Pacific and a secondary maximum in the east North Pacific. PTC-related heavy precipitation accounts for as much as 40% of the annual heavy precipitation in the northwest portion of the west North Pacific basin and 3.13% of heavy precipitation globally. We observe that the major hurricane stage contributes on average 2.6% of the global TC- and PTC-related precipitation, while the less intense but more common tropical storm stages of the TC life cycle contribute 85.7% of this observed precipitation. This analysis framework can be further extended to assess model biases and climate projections of TC and PTC precipitation.

Meteorology & Atmospheric Sciences↗

DOE OSTI2025

End-of-Century Changes in Orographic Precipitation with the Intermediate Complexity Atmospheric Research Model over the Western United States

Abstract Downscaled precipitation projections were created using the Intermediate Complexity Atmospheric Research (ICAR) model over the western United States to increase the physical realism in orographic precipitation changes. End-of-century simulations from eight models in phase 5 of the Coupled Model Intercomparison Project (CMIP5) were downscaled with ICAR and compared to the widely utilized statistically downscaled dataset, localized constructed analogs (LOCAs), to understand where and why projections of cool-season (September–May) precipitation differed. ICAR and LOCA precipitation projections were similar, but their sign differed in hydrologically relevant regions likely due to ICAR’s simulation of microphysics and mesoscale dynamics with high-resolution topography (6 km). In the Pacific Northwest, cool-season precipitation projections from ICAR showed an increase on the windward side of the Cascades and no significant change within the lee. This difference between the windward and leeward side was attributed to reduced zonal wind speeds, allowing more time for microphysical processes within ICAR. This contrast is enhanced by rain’s faster fall speed compared to snow, limiting transport into the lee. Meanwhile, LOCA projected an increase in precipitation across the Cascades. In the Upper Colorado River basin, LOCA projected an increase in precipitation in high elevation regions (>3000 m), but ICAR projected no significant change or a decrease in precipitation. High elevation differences were most evident in the spring and fall and were also attributed to a snow-to-rain transition and dynamical processes that impacted orographic enhancement within ICAR. Idealized, controlled studies are needed to better isolate individual processes, but these results underscore the importance of including microphysics and mesoscale dynamics within regional-scale precipitation projections. Significance Statement A set of global climate model simulations was downscaled using an atmospheric model that contains key physical equations, referred to as Intermediate Complexity Atmospheric Research (ICAR). ICAR was used to examine projected changes in end-of-century cool-season precipitation over mountains in the western United States. Precipitation projections from ICAR were similar to projections that used statistical relationships to downscale climate projections. However, projections differed between ICAR and statistically downscaled datasets in whether they increased, decreased, or stayed the same in specific, hydrologically relevant regions such as the eastern Cascades and high elevation areas of the Upper Colorado River basin. These differences were attributed to the simulation of physical processes in ICAR. The results highlight the importance of kilometer-scale atmospheric processes in regional climate projections.

Currier, William Ryan [NOAA/Physical Sciences Labo↗

DOE OSTI2019

Data from Assessing Precipitation, Evapotranspiration, and NDVI as Controls of U.S. Great Plains Plant Production

Productivity throughout the North American Great Plains grasslands is generally considered to be water limited, with the strength of this limitation increasing as precipitation decreases. We hypothesize that cumulative actual evapotranspiration water loss (AET) from April to July is the precipitation‐related variable most correlated to aboveground net primary production (ANPP) in the U.S. Great Plains (GP). We tested this by evaluating the relationship of ANPP to AET, precipitation, and plant transpiration (Tr). We used multi‐year ANPP data from five sites ranging from semiarid grasslands in Colorado and Wyoming to mesic grasslands in Nebraska and Kansas, mean annual NRCS ANPP, and satellite‐derived normalized difference vegetation index (NDVI) data. Results from the five sites showed that cumulative April‐to‐July AET, precipitation, and Tr were well correlated (R2: 0.54–0.70) to annual changes in ANPP for all but the wettest site. AET and Tr were better correlated to annual changes in ANPP compared to precipitation for the drier sites, and precipitation in August and September had little impact on productivity in drier sites. April‐to‐July cumulative precipitation was best correlated (R2 = 0.63) with interannual variability in ANPP in the most mesic site, while AET and Tr were poorly correlated with ANPP at this site. Cumulative growing season (May‐to‐September) NDVI (iNDVI) was strongly correlated with annual ANPP at the five sites (R2 = 0.90). Using iNDVI as a surrogate for ANPP, we found that county‐level cumulative April–July AET was more strongly correlated to ANPP than precipitation for more than 80% of the GP counties, with precipitation tending to perform better in the eastern more mesic portion of the GP. Including the ratio of AET to potential evapotranspiration (PET) improved the correlation of AET to both iNDVI and mean county‐level NRCS ANPP. Accounting for how different precipitation‐related variables control ANPP (AET in drier portion, precipitation in wetter portion) provides opportunity to develop spatially explicit forecasting of ANPP across the GP for enhancing decision‐making by land managers and use of grassland ANPP for biofuels.

Field Data↗

DOE OSTI2018

Final Report on "Collaborative Research to Narrow Uncertainties in Precipitation and the Hydrological Cycle in Climate Models"

The central objectives of this work have been to explore and improve the depiction of precipitation and related processes in climate models by developing and analyzing observations and their gridded analyses, and developing new approaches and metrics. All three groups worked with the NCAR-based Community Earth System Model (CESM) and international community Climate Model Inter-comparison Project version 5 (CMIP5) models in various ways. At NCAR and SUNYA an initial focus was on the observational record, including updating of the river discharge dataset. A major focus at NCAR was extensive work on new datasets of hourly precipitation from CMORPH (observations) and CESM, and commentary on and validation of the CESM. SUNYA contributed to the comparison and evaluation of existing precipitation products widely used in climate research, the analysis of precipitation characteristics in CESM and other CMIP5 models, and decadal precipitation variability associated with decadal variability. At NCAR and SUNYA work was focused on the frequency and intensity of precipitation, including their dependence on the temporal and spatial resolution of the data used to calculate the frequency and intensity, as well as additional analyses on the effects of precipitation data uncertainties on the estimated historical drying trends. LLNL focused on the diurnal cycle. New insights have resulted in the characteristics of precipitation (frequency, intensity, amount, duration, diurnal cycle, covariability in space and time) and evaluation of these in models. In general models perform poorly and this provides a much-needed focus on what aspects of models are greatly in need of improvement. A substantial number of papers have now been published on these topics. The focus on the characteristics of precipitation and not just amount also provides a natural entrée into examining the extremes of precipitation, that are very important to the general public in terms of impacts. Examples are the deluges from Florence and Harvey, and extensive work has been performed on the latter. On the other side of the coin, considerable work has been performed on dry spells and drought, including improvements in a drought index. There has been considerable outreach to the general public, especially through the media, but also via talks and lectures, and a strong educational component at SUNYA. For example, the Harvey paper has an altimetrics rating of 827 and is the highest for any paper from that journal, it is at the 99th percentile of all papers of the same age, and is in the top 95 percent of all papers. The energy cycle and ocean heat content has been another focus. The entire atmospheric energy cycle has been reformulated and applied to the latest data to include effects from the enthalpy of precipitation. Relationships between ocean heat content and sea level rise have also been extensively explored in observations and models, with new insights into the role of Mount Pinatubo volcanic eruption on distorting and hiding the accelerating sea level rise. This work has been also widely featured in news media. The “year without a summer” has also been explored in the past using models, and how changes in the vertical structure and stability of the ocean with a warming climate may influence a future such volcanic event by amplifying the surface temperature response.

58 GEOSCIENCES↗

DOE OSTI2021

Application of Point Precipitation Frequency Estimates to Watersheds

This report documents work sponsored by the U.S. Nuclear Regulatory Commission (NRC) at the Oak Ridge National Laboratory (ORNL) as part of the RES project, “Application of Point Precipitation Frequency Estimates to Watersheds.” This project was implemented as part of the Probabilistic Flood Hazard Assessment (PFHA) Research Program. The objective of the PFHA Research Program is to develop tools and guidance on the use of PFHA methods to risk-inform NRC’s licensing of new facilities as well as licensing and oversight of currently operating facilities as they relate to flooding hazards. Many nuclear power plants (NPPs) are located on or near rivers so riverine flooding hazards need to be considered in their design and operation. Probabilistic riverine flood models are important tools for realistic assessment of flooding risks. However, these models require areal estimates of the depth, duration, and frequency of rainfall distributed over the watershed, which are not often available. Point precipitation frequency estimates are more widely available. For example, the National Oceanic and Atmospheric Administration (NOAA) has published NOAA Atlas 14, which provides point precipitation frequency estimates for 5-minute through 60-day durations at average recurrence intervals of 1-year through 1,000-year. The research documented in this report addresses areal reduction factors (ARFs), which can be used to convert the widely available point precipitation frequency estimates, to estimates of areal precipitation frequency over a watershed. The most widely used ARF source is Technical Paper 29 (TP-29) published by the then U.S. Weather Bureau in 1958. However, both the methods and the underlying precipitation data used to produce TP-29 are seriously out of date. For example, due to the small gauge network available at the time of TP-29’s compilation, ARF estimates developed are only for watersheds smaller than about 400 square miles. Due to the relatively short record lengths of precipitation data available, frequency considerations could not be accurately determined. Other factors such as regional climate and seasonality were not addressed. Several newer methods have been published since TP-29 was developed and both the type and quantity of precipitation data have increased significantly, along with computational resources and analytical tools such as geographic information systems. This report reviewed and assessed the available precipitation products and methods for conducting ARF analysis. The work applied up-to-date precipitation data products and analysis methods with a novel watershed-based approach to investigate how ARF estimates vary across different methods, data sources, geographical locations, return periods, and seasons. The overall findings reported here regarding basic ARF trends are in line with other recent studies showing that ARFs decrease with increasing area, increase with increasing duration, and decrease with increasing return period. This study found significant differences among the available ARF methods. This work also found a strong geographical variability across different US hydrologic regions, suggesting that the ARF are specific to regional climate patterns and geographical characteristics and should not be applied arbitrarily to other locations. The results also reveal the importance of data record length, especially for high return level ARFs. The work reported in NUREG/CR-7271 will assist NRC staff in assessing different classes of ARF methods in conjunction with available rainfall data sets. It will also support the development of guidance for application of point precipitation data in PFHAs. It should be noted that the ARF values presented in this report for any location or region were developed for the purposes of comparing methods and investigating the factors that influence ARFs. They should not be considered official and should not be used in leu of a site-specific analysis.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Earth-system-model evaluation of cloud and precipitation occurrence for supercooled and warm clouds over the Southern Ocean's Macquarie Island

Abstract. Over the remote Southern Ocean (SO), cloud feedbacks contribute substantially to Earth system model (ESM) radiative biases. The evolution of low Southern Ocean clouds (cloud-top heights < ∼ 3 km) is strongly modulated by precipitation and/or evaporation, which act as the primary sink of cloud condensate. Constraining precipitation processes in ESMs requires robust observations suitable for process-level evaluations. A year-long subset (April 2016–March 2017) of ground-based profiling instrumentation deployed during the Macquarie Island Cloud and Radiation Experiment (MICRE) field campaign (54.5∘ S, 158.9∘ E) combines a 95 GHz (W-band) Doppler cloud radar, two lidar ceilometers, and balloon-borne soundings to quantify the occurrence frequency of precipitation from the liquid-phase cloud base. Liquid-based clouds at Macquarie Island precipitate ∼ 70 % of the time, with deeper and colder clouds precipitating more frequently and at a higher intensity compared to thinner and warmer clouds. Supercooled cloud layers precipitate more readily than layers with cloud-top temperatures > 0 ∘C, regardless of the geometric thickness of the layer, and also evaporate more frequently. We further demonstrate an approach to employ these observational constraints for evaluation of a 9-year GISS-ModelE3 ESM simulation. Model output is processed through the Earth Model Column Collaboratory (EMC2) radar and lidar instrument simulator with the same instrument specifications as those deployed during MICRE, therefore accounting for instrument sensitivities and ensuring a coherent comparison. Relative to MICRE observations, the ESM produces a smaller cloud occurrence frequency, smaller precipitation occurrence frequency, and greater sub-cloud evaporation. The lower precipitation occurrence frequency by the ESM relative to MICRE contrasts with numerous studies that suggest a ubiquitous bias by ESMs to precipitate too frequently over the SO when compared with satellite-based observations, likely owing to sensitivity limitations of spaceborne instrumentation and different sampling methodologies for ground- versus space-based observations. Despite these deficiencies, the ESM reproduces the observed tendency for deeper and colder clouds to precipitate more frequently and at a higher intensity. The ESM also reproduces specific cloud regimes, including near-surface clouds that account for ∼ 25 % of liquid-based clouds during MICRE and optically thin, non-precipitating clouds that account for ∼ 27 % of clouds with bases higher than 250 m. We suggest that the demonstrated framework, which merges observations with appropriately constrained model output, is a valuable approach to evaluate processes responsible for cloud radiative feedbacks in ESMs.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2019

Characterization of shallow oceanic precipitation using profiling and scanning radar observations at the Eastern North Atlantic ARM observatory

Shallow oceanic precipitation variability is documented using three second-generation radar systems located at the Atmospheric Radiation Measurement (ARM) Eastern North Atlantic observatory: ARM zenith radar (KAZR2), the Ka-band scanning ARM cloud radar (KaSACR2) and the X-band scanning ARM precipitation radar (XSAPR2). First, the radar systems and measurement post-processing techniques, including sea-clutter removal and calibration against colocated disdrometer and Global Precipitation Mission (GPM) observations are described. Then, we present how a combination of profiling radar and lidar observations can be used to estimate adaptive (in both time and height) parameters that relate radar reflectivity (Z) to precipitation rate (R) in the form Z=αR β , which we use to estimate precipitation rate over the domain observed by XSAPR2. Furthermore, constant altitude plan position indicator (CAPPI) gridded XSAPR2 precipitation rate maps are also constructed. Hourly precipitation rate statistics estimated from the three radar systems differ because KAZR2 is more sensitive to shallow virga and XSAPR2 suffers from less attenuation than KaSACR2 and as such is best suited for characterizing intermittent and mesoscale-organized precipitation. Further analysis reveals that precipitation rate statistics obtained by averaging 12 h of KAZR2 observations can be used to approximate that of a 40 km radius domain averaged over similar time periods. However, it was determined that KAZR2 is unsuitable for characterizing domain-averaged precipitation rate over shorter periods. But even more fundamentally, these results suggest that these observations cannot produce an objective domain precipitation estimate and that the simultaneous use of forward simulators is desirable to guide model evaluation studies.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2016

On the controls of daytime precipitation in the Amazonian dry season

The Amazon plays an important role in the global energy and hydrological budgets. The precipitation during the dry season (June–September) plays a critical role in maintaining the extent of the rain forest. The deployment of the first Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF-1) in the context of the Green Ocean Amazon (GOAmazon) field campaign at Manacapuru, Brazil, provided comprehensive measurements of surface, cloud, precipitation, radiation, and thermodynamic properties for two complete dry seasons (2014 and 2015). The precipitation events occurring during the nighttime were associated with propagating storm systems (nonlocal effects), while the daytime precipitation events were primarily a result of local land–atmosphere interactions. During the two dry seasons, precipitation was recorded at the surface on 106 days (43%) from 158 rain events with 82 daytime precipitation events occurring on 64 days (60.37%). Detailed comparisons between the diurnal cycles of surface and profile properties between days with and without daytime precipitation suggested the increased moisture at low and midlevels to be responsible for lowering the lifting condensation level, reducing convective inhibition and entrainment, and thus triggering the transition from shallow to deep convection. Although the monthly accumulated rainfall decreased during the progression of the dry season, the contribution of daytime precipitation to it increased, suggesting the decrease to be mainly due to reduction in propagating squall lines. Lastly, the control of daytime precipitation during the dry season on large-scale moisture advection above the boundary layer and the total rainfall on propagating squall lines suggests that coarse-resolution models should be able to accurately simulate the dry season precipitation over the Amazon basin.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Legacies of precipitation influence primary production in Panicum virgatum

Precipitation is a key driver of primary production worldwide, but primary production does not always track year-to-year variation in precipitation linearly. Instead, plant responses to changes in precipitation may exhibit time lags, or legacies of past precipitation. Legacies can be driven by multiple mechanisms, including persistent changes in plant physiological and morphological traits and changes to the physical environment, such as plant access to soil water. Here, we used three precipitation manipulation experiments in central Texas, USA to evaluate the magnitude, duration, and potential mechanisms driving precipitation legacies on aboveground primary production of the perennial C 4 grass, Panicum virgatum. Specifically, we performed a rainout shelter study, where eight genotypes grew under different precipitation regimes; a transplant study, where plants that had previously grown in a rainout shelter under different precipitation regimes were moved to a common environment; and a mesocosm study, where the effect of swapping precipitation regime was examined with a single genotype. Across these experiments, plants previously grown under wet conditions generally performed better than expected when exposed to drought. Panicum virgatum exhibited stronger productivity legacies of past wet years on current-year responses to drought than of past dry years on current-year responses to wet conditions. Additionally, previous year tiller counts, a proxy for meristem availability, were important in determining legacy effects on aboveground production. As climate changes and precipitation extremes—both dry and wet—become more common, these results suggest that populations of P. virgatum may become less resilient.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2012

Effects of internal stresses and intermediate phases on the coarsening of coherent precipitates: A phase-field study

Phase stability, topology and size evolution of precipitates are important factors in determining the mechanical properties of crystalline materials. In this article, the Cahn-Hilliard type of phase-field model was coupled to elasticity equations within a mixed-order Galerkin finite element framework to study the coarsening morphology of coherent precipitates. The effects of capillarity, particle size and fraction, compositional strain, and inhomogeneous elasticity on the kinetics and kinematics of coherent precipitates in a binary dual phase crystal admitting a third intermediate stable/meta-stable phase were investigated. The results demonstrated the ability of the model to simulate coarsening under the concomitant action of Ostwald ripening and mismatch elastic strain mechanisms. Using a phenomenological coarsening power law, coarsening rates were determined to depend on precipitate size and volume fraction, compositional strain, and strain mismatch between precipitates and the matrix. Results also showed that the necking incubation time between two neighboring precipitates depends inversely on the precipitate's initial sizes; however, under fixed volume fraction of precipitates, any increase in the initial sizes of the precipitates mitigates the coarsening. Meanwhile, the compositional strain and the growth of the intermediate stable/meta-stable phase leads to substantial enhancements of precipitate coarsening.

36 MATERIALS SCIENCE↗

DOE OSTI2020

On the use of charged particles to characterize precipitation in irradiated reactor pressure vessel steels with a wide range of compositions

Nuclear reactor lifetimes may be limited by nano-scale Cu-Mn-Ni-Si precipitates (CRPs and MNSPs) that form under neutron irradiation (NI) of pressure vessel (RPV) steels, resulting in hardening and ductile to brittle transition temperature increases (embrittlement). Physical models of embrittlement must be based on characterization of precipitation as a function of the combination of metallurgical and irradiation variables. Here we focus on rapid and convenient charged particle irradiations (CPI) to both: a) compare to precipitates formed in NI; and, b) use CPI to efficiently explore precipitation in steels with a very wide range of compositions. Atom probe tomography (APT) comparisons show NI and CPI for similar bulk steel solute contents yield nearly the same precipitate compositions, albeit with some differences in their number density, size and volume fraction (f) dose (dpa) dependence. Yet, the overall precipitate evolutions are very similar. Advanced high Ni (>3 wt%) RPV steels, with superior unirradiated properties, were also investigated at high CPI dpa. For typical Mn contents, MNSPs have Ni 16 Mn 6 Si 7 or Ni 3 Mn 2 Si phase type compositions, with f values that are close to the equilibrium phase separated values. In contrast, in steels with very low Mn and high Ni, Ni 2-3 Si silicide phase type precipitate compositions are observed; and when Ni is low, the precipitate compositions are close to the MnSi phase field. Low Mn significantly reduces, but does not eliminate, precipitation in high Ni steels. A comparison of dispersed barrier model predictions with measured hardening data suggests that the Ni-Si dominated precipitates are weaker dislocation obstacles than the G phase type MNSPs.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2014

Elemental segregation and subsequent precipitation during solidification of continuous cast Nb–V–Ti high-strength low-alloy steels

In this study, elemental segregation during solidification and subsequent precipitation behaviour in a continuous cast Nb–V–Ti high-strength low-alloy steel was investigated by optical microscopy, scanning electron microscopy with energy dispersive X-ray spectroscopy and thermodynamic modelling. It is known that for steels with low carbon contents the pearlite that forms on slow cooling does so where the interdendritic liquid was present prior to final solidification. The alloying elements of Nb, Ti, Mn and V segregate into the interdendritic liquid during solidification, while Al preferentially segregates into the solidifying solid phase. The composition analysis on the slab samples verified the predicted element segregation behaviour, with a smaller difference in the concentrations of Mn and V in the pearlite and dendritic ferrite regions being observed compared to the Nb levels. Small (30–100 nm) spherical or irregular shaped Nb-rich precipitates (Nb(C, N) and (Nb, V)(C, N)) were mainly found in the pearlite regions, while angular Al-rich (60–300 nm) precipitates were found in the dendritic ferrite regions, in the form of AlN and complex AlN–V(C, N) precipitates. Small isolated ferrite regions surrounded by pearlite were observed in the microstructure and has two origins: one type is dendritic ferrite that appears as an isolated island due to a sectioning effect when observing the two-dimensional microstructure; the other is a ferrite idiomorph that forms in the interdendritic region due to the low carbon content of the steel. Accordingly, in these isolated ferrite islands two different precipitation behaviours are found; predominantly Al-rich particles in the dendritic regions or predominantly Nb-rich precipitates in the interdendritic ferrite idiomorphs. No Al-rich precipitates were observed in the interdendritic regions (pearlite or isolated ferrite idiomorphs) despite the Thermo-Calc predictions indicating a higher volume fraction of AlN in these regions compared to the dendritic regions. This is believed to be due to back diffusion of nitrogen after solidification reducing the available nitrogen, which reacts with the high Nb levels present. - Highlights: • Nb-rich precipitates (Nb(C, N) and (Nb, V)(C, N)) were mainly found in pearlite. • Angular Al-rich precipitates (AlN and AlN–V(C, N)) were found in dendritic ferrite. • Precipitation behaviour in isolated ferrite islands within pearlite was revealed. • Segregation of substitutional elements during solidification is retained. • Back diffusion of interstitial elements (C, N) occurred.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Effects of combined silicon and molybdenum alloying on the size and evolution of microalloy precipitates in HSLA steels containing niobium and titanium

The effects of combined silicon and molybdenum alloying additions on microalloy precipitate formation in austenite after single- and double-step deformations below the austenite no-recrystallization temperature were examined in high-strength low-alloy (HSLA) steels microalloyed with titanium and niobium. The precipitation sequence in austenite was evaluated following an interrupted thermomechanical processing simulation using transmission electron microscopy. Large (~ 105 nm), cuboidal titanium-rich nitride precipitates showed no evolution in size during reheating and simulated thermomechanical processing. The average size and size distribution of these precipitates were also not affected by the combined silicon and molybdenum additions or by deformation. Relatively fine (< 20 nm), irregular-shaped niobium-rich carbonitride precipitates formed in austenite during isothermal holding at 1173 K. Based upon analysis that incorporated precipitate growth and coarsening models, the combined silicon and molybdenum additions were considered to increase the diffusivity of niobium in austenite by over 30% and result in coarser precipitates at 1173 K compared to the lower alloyed steel. Deformation decreased the size of the niobium-rich carbonitride precipitates that formed in austenite. - Highlights: • We examine combined Si and Mo additions on microalloy precipitation in austenite. • Precipitate size tends to decrease with increasing deformation steps. • Combined Si and Mo alloying additions increase the diffusivity of Nb in austenite.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Influence of cooling rate on the precipitation behavior in Ti–Nb–Mo microalloyed steels during continuous cooling and relationship to strength

In this study we elucidate carbide precipitation at varied cooling rates in Ti–Nb–Mo microalloyed steels during continuous cooling. The study suggests that increasing the cooling rate prevents precipitate formation in the ferrite phase during continuous cooling after finish rolling at 850 °C. At a lower cooling rate of 0.5 °C/s, the microhardness of ferrite grains exhibited maxima because of high volume fraction of fine carbides. A high density of nanoscale carbides with similar precipitation characteristics, including interphase precipitates, was observed at cooling rates of 0.5 and 1 °C/s, but the carbides were marginally larger and the spacing between them was increased with cooling rate. Additionally, carbide precipitation at a high cooling rate was associated with strain-induced precipitation. Through the analysis of selection area electron diffraction patterns and high-resolution transmission electron microscopy, lattice imaging, the fine spherical-shaped carbides of size ~ 6–10 nm were identified as MC-type carbides of the type (Ti,Nb,Mo)C and NbC. - Highlights: • We model three cooling rates which have indicated different precipitation behaviors. • We find two types of precipitates including NbC and (Ti,Nb,Mo)C based on HRTEM study. • Increasing cooling rate will decrease volume fraction and size of the precipitates. • There is no absence of interphase precipitation when the cooling rate increases to 5 °C/s.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Characterizing precipitate evolution of an Al–Zn–Mg–Cu-based commercial alloy during artificial aging and non-isothermal heat treatments by in situ electrical resistivity monitoring

In situ electrical resistivity monitoring technique was employed to continuously evaluate the precipitate evolution of an Al–Zn–Mg–Cu-based commercial alloy during typical artificial aging treatments. The effects of artificial aging on the precipitates stability during non-isothermal heat treatments were also explored. Conventional hardness test, transmission electron microscopy and differential scanning calorimetry were also adopted to verify the electrical resistivity results. The results indicated that both the precipitation process and its timely rate could be followed by the monitored electrical resistivity during artificial aging treatments. The electrical resistivity results gave overall information on continuous precipitation and dissolution processes, especially under high heating rates. Samples artificial aging heat treated at 120 °C for 24 h followed by aging at 150 °C for 24 h presented more stable state and coarser precipitates than the samples only artificial aging heat treated at 120 °C for 24 h or triple artificial aging heat treated at 120 °C/24 h + 195 °C/15 min + 120 °/24 h. While the incoherent η precipitates in the samples artificial aging heat treated at 120 °C for 24 h followed by aging at 150 °C for 24 h were more easiness to coarsening and dissolve during non-isothermal heat treatments as well. - Highlights: • In situ electrical resistivity monitoring technique was employed on an Al-Zn-Mg-Cu alloy. • The precipitate evolution during typical artificial aging treatments was studied. • The precipitate stability during non-isothermal heat treatments was explored. • The electrical resistivity wonderfully monitored continuous precipitation and dissolution. • The alloy submitted to a T7 treatment presents a more stable state during heating due to incoherent η precipitates.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Sulfide precipitation characteristics of Mn, Ni, Co, and Zn in the presence of contaminant metal ions

In this study, the effects of Al 3+ and Fe 2+ on the precipitation characteristics of four valuable metals, including Mn 2+ , Ni 2+ , Co 2+ , and Zn 2+ , were investigated by conducting solution chemistry calculations, sulfide precipitation tests, and mineralogy characterizations. It was found that the ability of the valuable metals to form sulfide precipitates followed an order of Zn 2+ > Ni 2+ > Co 2+ > Mn 2+ . The sulfide precipitate of Zn 2+ was the most stable and did not re-dissolve under the acidic condition (pH 4.00 ± 0.05). In addition, the sulfide precipitation characteristics of Zn 2+ was barely affected by the contaminant metal ions. However, in the presence of Al 3+ , the precipitation recoveries of Mn 2+ , Ni 2+ , and Co 2+ were noticeably reduced due to simultaneous hydrolysis and competitive adsorption. The precipitation recoveries of Ni 2+ and Co 2+ in solutions containing individual valuable metals also reduced when Fe 2+ was present, primarily due to competitive precipitation. However, the recovery of Mn 2+ was enhanced due to the formation of ferrous sulfide precipitate, providing abundant active adsorption sites for Mn species. Here, in the solution containing all the valuable metals, Fe 2+ promoted the recovery of the valuable metals due to the higher concentration of Na 2 S and the formation of ferrous sulfide precipitate.

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